非支链氧化:低反应性RO•4和HO•4 1:2加合自由基缩短动力学链

M. M. Silaev
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引用次数: 1

摘要

提出了一种新的非支链自由基加成到分子氧多键上的反应方案。该方案包括通过活性自由基与链传播反应竞争的反应。该方案的链演化阶段涉及少量自由基,其中一种自由基(四氧基)反应性较低,通过缩短动力学链长来抑制链过程。在此基础上,采用准稳态处理方法推导了速率方程(包含1 ~ 3个直接确定的参数)。利用所得到的速率方程的动力学描述,应用于373 K时液态邻二甲苯自由基氧化和296 K时含不同氧量的水中氢的非支链反应。在这些过程中,随着氧浓度的增加,氧开始起氧化自燃剂(或抗氧化剂)的作用,过氧化物形成速率作为溶解氧浓度的函数有一个最大值。比较了简单烷基过氧基(放热)和烷基氧基(吸热)自由基在气相中解离总反应的热效应。从能量的角度来看,自由基氧化氢的可能的非链途径和臭氧衰变的途径通过与上层大气中的羟基自由基的反应(包括加成产生氢四氧自由基,它可以是生物有害紫外线辐射能量转换序列的中间物)进行了检查。考虑了关键的自由基-分子反应的能量学。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Nonbranched-Chain Oxidation: Low-Reactive RO•4 and HO•4 1:2 Adduct Radicals Shortening Kinetic Chains
New reaction scheme is suggested for the initiated nonbranched-chain addition of free radicals to the multiple bond of the molecular oxygen. The scheme includes the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which (tetraoxyl) is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the proposed scheme rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the I³-induced nonbranched-chain processes of the free-radical oxidation of liquid o -xylene at 373 K and hydrogen dissolved in water containing different amounts of oxygen at 296 K. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. The heat effects are compared for the overall reactions of dissociation of simple alkylperoxyl (exothermic) and alkoxyl (endothermic) free radicals in the gas phase. Possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay from the energetic standpoint via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule reactions is considered.
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